CN104691067A - Biodegradable multilayer material with adjustable gas transmission rate and preparation method and applications thereof - Google Patents
Biodegradable multilayer material with adjustable gas transmission rate and preparation method and applications thereof Download PDFInfo
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- CN104691067A CN104691067A CN201510099970.6A CN201510099970A CN104691067A CN 104691067 A CN104691067 A CN 104691067A CN 201510099970 A CN201510099970 A CN 201510099970A CN 104691067 A CN104691067 A CN 104691067A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to a biodegradable multilayer material, which can be a thin film material or a sheet material. The biodegradable multilayer material at least comprises one of an adipic butanediol terephthalate copolymer (PBAT)/PBAT-chain extender-polypropylene carbonate (PBAT-Co-PPC)/PPC blend layer, a PBAT/PBAT-chain extender-polylactic acid (PBAT-Co-PLA)/PLA blend layer and a PBAT/PBAT-chain extender-polyhydroxyalkanoate (PBAT-Co-PHA)/PHA blend layer, and blend resins are respectively prepared through twin-screw reactive extrusion. The multilayer material is produced by using extrusion and coextrusion methods, has a function that the transmission rates of oxygen, carbon dioxide and water vapor can be adjusted, and can be applied to the packaging field and the agriculture field, and especially applied to food packaging, pharmaceutical packaging, and ground film mulching.
Description
Technical field
This technology relates to a kind of biodegradable multilayered film material or sheeting, it has the adjustable function of oxygen, carbon dioxide and water vapour permeability, can be used for packaging field, agriculture field, especially for packaging for foodstuff, medical packaging, covered ground film.
Background technology
After conventional plastic packaging uses, utilize owing to not being recovered or being arbitrarily discarded in natural environment in large quantities because of not easily reclaiming, cause pollution to environment, therefore Biodegradable material and packing articles thereof become the focus of current research and development gradually.If specify that a kind of homogenous material is tested according to GB/T 19277.1 in China standard GB/T/T20197, its biological decomposition rate is Biodegradable material 60% time.Up to now; the biodegradable plastic kind of scale or pilot scale has PLA (PLA), PHA (PHA; comprise PHB, PHBV, P (3HB, 4HB) and PHBH etc.), poly-succinic fourth diester (PBS), terephthalic acid (TPA) adipic acid butanediol copolymer (PBAT), poly-succinic-adipic acid-Ding diester (PBSA), poly (propylene carbonate) (PPC), polycaprolactone (PCL) etc.
As packaging material, especially the plastic package material of food, medicine will be used for, General Requirements its have good barrier as oxygen-barrier property, carbon dioxide barrier, water vapor barrier etc., and when breathing the packaging of food for fresh vegetables, fruit etc. containing son, more require its oxygen through, carbon dioxide through and water vapour permeability can regulate and control.
At present, the single creature degradable materials such as PLA, PHA, PPC, PBAT, PBS, there is certain defect in its barrier, or OTR oxygen transmission rate is too high, or carbon dioxide transmitance is too high, or water vapour permeability is too high, and the obstruct requirement of packaged food or medicine can not be met, thus delay the progress substituting Traditional Packing satisfactorily.Utilize different biodegradation material Gas permeability separately, after its compound is obtained multilayer material, the barrier property of material can be improved, and realize the adjustable object of gas permeation rate.But at present, about the relevant report of biodegradable, that gas permeation rate is adjustable multilayered film material or composite wafer is little.
CN200380105492.0 reports a kind of plural layers of Biodegradable altogether, it primarily of containing the starch mixture layer of 1-10% and biodegradable polyesters layer through the multi-layer co-extruded plural layers obtained, although can play in this application Patent right requirement, oxygen, nitrogen, carbon dioxide and water vapour are intercepted, but there are some shortcomings in it: containing starch mixture in (1) formula, need to carry out thermoplastic modification to starch, and the interpolation of starch makes the physical property of integral material decline, long-term storage is deteriorated; (2) Biodegradable polyester layer is the mixing of various simple aggregation thing, is physical mixed completely and compatibility is poor, so will add the auxiliary agents such as some compatilizers to make up these defects between polymer; (3) although plural layers can be formed by more than two layers, but can only optimum selecting three-layer, reason be layer by layer between need to realize compatibility by starch mixture or softening agent etc., which increase difficulty of processing, and these compatilizers can affect the performance of product after easily moving or separating out; (4) material used by plural layers is not owing to having the good biodegradation material of this class oxygen-barrier property of poly (propylene carbonate), so do not utilize this kind of material of poly (propylene carbonate) in CN200380105492.0 when fashion; (5) finished product of plural layers has less permeability, has barrier effect to nitrogen, carbon dioxide and water vapour due to obstruct aspect, just play stop and degraded through effect, and adjustments of gas can not be carried out needed for packaging fresh food and adjust through size.Exactly because exist above not enough, the long term storage performance of this patent requirements product processes relative complex, product is poor, so commercially can't see this series products at present.
CN201310682547.X reports a kind of high barrier complete biodegradable composite membrane, this composite membrane is three-decker, and skin is made up of 75-90% poly terephthalic acid-adipic acid-butanediol ester (PBAT) and poly-(adipic acid-butanediol ester-co-trimethylene carbonic ester) copolymer (PBA-co-PC) of 10-25%; Intermediate layer polypropylene carbonate (PPC) material, inner layer material is made up of 80-95% PLA (PLA) and poly-(lactic acid-trimethylene carbonic ester) copolymer (PLA-co-PC) of 5-20%.Although this technical products is improved due to material barrier after three layers of compound, but there is following shortcoming: (1) just have employed PPC layer due to intermediate layer, ectonexine adopts PBA-Co-PC, PLA-Co-PC as compatilizer respectively, so material can only be three-layer co-extruded; (2) because intermediate layer is only PPC, and the vitrification point of PPC only has 35 DEG C, in the situation such as room temperature in summer, be easy to distortion, so multi-layered product becomes quality instability due to intermediate layer distortion; (3) PBA-Co-PC, PLA-Co-PC copolymer adopts and is chain extender and adopts routine techniques to be polymerized to obtain with isocyanates, so technique needs Macroscopic single crystal technique, and relative complex, and accessory substance is more; (4) because intermediate layer is fixed as PPC layer, improve so composite membrane just can play barrier, but be difficult to realize the selective controllability of gas-premeable; (5) owing to adopting isocyanates to be chain extender, so be restricted when composite membrane is used for packaging for foodstuff.
In addition, also the multi-layer co-extruded material that some reports are primary raw material with conventional plastic such as polyethylene is had, declare to breathe freely and can be in harmonious proportion degraded, but actual is can not complete biodegradable, can only confuse right and wrong, therefore, develop that a kind of gas-premeable is adjustable, physical property is stablized and the multilayer material of complete biodegradable can seem particularly important and necessary.
Summary of the invention
The object of this invention is to provide the adjustable multilayer material of a kind of gas permeation rate (comprising film and thin slice), simultaneously can complete biodegradable, can be used for packaging material and the goods such as packaging for foodstuff, medical packaging, agriculture covered ground film, daily plastic bag.
Multilayer material of the present invention can be three layers or five layers or seven-layer structure, and the one wherein at least comprising following material is formed:
(1) terephthalic acid (TPA) adipic acid butanediol copolymer (PBAT)/terephthalic acid (TPA) adipic acid butanediol copolymer-chain extender--poly (propylene carbonate) (PBAT-Co-PPC)/poly (propylene carbonate) (PPC) blend layer (PBAT/PBAT-Co-PPC/PPC), in PBAT/PBAT-Co-PPC/PPC layer, each constituent mass percentage composition is PBAT is 20 ~ 80%, PBAT-Co-PPC is 1 ~ 20%, PPC is 20 ~ 80%;
(2) terephthalic acid (TPA) adipic acid butanediol copolymer (PBAT)/terephthalic acid (TPA) adipic acid butanediol copolymer-chain extender-PLA (PBAT-Co-PLA)/PLA (PLA) blend layer (PBAT/PBAT-Co-PLA/PLA), in PBAT/PBAT-Co-PLA/PLA layer, each constituent mass percentage composition is PBAT is 40 ~ 80%, PBAT-Co-PLA is 1 ~ 20%, PLA is 20 ~ 60%;
(3) terephthalic acid (TPA) adipic acid butanediol copolymer (PBAT)/terephthalic acid (TPA) adipic acid butanediol copolymer-chain extender-PHA (PBAT-Co-PHA)/PHA (PHA) blend layer (PBAT/PBAT-Co-PHA/PHA), in PBAT/PBAT-Co-PHA/PHA layer, each constituent mass percentage composition is PBAT is 20 ~ 80%, PBAT-Co-PHA is 1 ~ 20%, PHA is 20 ~ 80%.
Described multilayer material PBAT/PBAT-Co-PPC/PPC blending resin, PBAT/PBAT-Co-PLA/PLA blending resin, PBAT/PBAT-Co-PHA/PHA blending resin is obtained by multi-layer co-extruded extrusion way respectively.When material is plural layers, by extruding coextrusion casting method or producing by extruding coextrusion blow forming method.When product is composite wafer, produce by extruding coextrusion casting forming method.
During described multilayer material co-extrusion, PBAT/PBAT-Co-PPC/PPC layer is in most intermediate layer.When material is three-layer co-extruded, PBAT/PBAT-Co-PPC/PPC is in most intermediate layer; During five-layer co-squeezing, PBAT/PBAT-Co-PPC/PPC layer is respectively second and the 4th layer (being followed successively by ground floor to layer 5 to innermost layer by surface); During seven-layer co-extrusion, PBAT/PBAT-Co-PPC/PPC layer respectively second, the 4th and layer 6 (being followed successively by ground floor to layer 7 to innermost layer by surface).
Described PBAT/PBAT-Co-PPC/PPC blending resin is that in double screw extruder, reactive extrursion granulation obtains by just Biodegradable resin PBAT, PPC is after interpolation chain extender.Material quality percentage composition is PBAT is 20 ~ 80%, PPC is 20 ~ 80%, chain extender consumption is 0.1 ~ 10%, and in the PBAT/PBAT-Co-PPC/PPC blending resin of acquisition, PBAT is 20 ~ 80%, PPC is 20 ~ 80%, PBAT-Co-PPC is 1 ~ 20%.In blend, the role of PBAT-Co-PPC is inner compatilizer, it not only serves the effect of increase-volume between PBAT and PPC in the blend, also be when multi-layer co-extruded simultaneously, make blend layer can be well compatible with adjacent bed, thus make multilayer material between layers in conjunction with tight and unlikely stripping or layering.
Described PBAT/PBAT-Co-PLA/PLA blending resin is that in double screw extruder, reactive extrursion granulation obtains by just Biodegradable resin PBAT, PLA is after interpolation chain extender.Material quality percentage composition is PBAT is 20 ~ 80%, PLA is 20 ~ 80%, chain extender consumption is 0.1 ~ 10%, and in the PBAT/PBAT-Co-PLA/PLA blending resin of acquisition, PBAT is 20 ~ 80%, PLA is 20 ~ 80%, PBAT-Co-PLA is 1 ~ 20%.In blend, the role of PBAT-Co-PLA is inner compatilizer, it not only serves the effect of increase-volume between PBAT and PLA in the blend, also be when multi-layer co-extruded simultaneously, make blend layer can be well compatible with intermediate layer (PBAT/PBAT-Co-PPC/PPC layer), thus make multilayer material between layers in conjunction with tight and unlikely stripping or layering.
Described PBAT/PBAT-Co-PHA/PHA blending resin, be that in double screw extruder, reactive extrursion granulation obtains by just Biodegradable resin PBAT, PHA is after interpolation chain extender.Material quality percentage composition is PBAT is 20 ~ 80%, PHA is 20 ~ 80%, chain extender consumption is 0.1 ~ 10%, and in the PBAT/PBAT-Co-PHA/PHA blending resin of acquisition, PBAT is 20 ~ 80%, PHA is 20 ~ 80%, PBAT-Co-PHA is 1 ~ 20%.In blend, the role of PBAT-Co-PHA is inner compatilizer, it not only serves the effect of increase-volume between PBAT and PHA in the blend, also be when multi-layer co-extruded simultaneously, make blend layer can be well compatible with intermediate layer (PBAT/PBAT-Co-PPC/PPC layer), thus make multilayer material between layers in conjunction with tight and unlikely stripping or layering.
Described chain extender can be at least one in polyoxyethylene poly-oxygen propylene aether block copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer, epoxies reactive compatibilizer, oxazoline class reactive compatibilizer, food-grade isocyanates reactive compatibilizer.
The thickness of described plural layers is 0.018 ~ 0.250mm, wherein, the every layer thickness of PBAT/PBAT-Co-PPC/PPC layer is 0.006 ~ 0.050mm, the every layer thickness of PBAT/PBAT-Co-PLA/PLA layer is the every layer thickness of 0.006 ~ 0.050mm, PBAT/PBAT-Co-PHA/PHA layer is 0.006 ~ 0.050mm.
The thickness of described composite wafer is 0.200 ~ 1.0mm, wherein, the every layer thickness of PBAT/PBAT-Co-PPC/PPC layer is 0.060 ~ 0.600mm, the every layer thickness of PBAT/PBAT-Co-PLA/PLA layer is the every layer thickness of 0.060 ~ 0.800mm, PBAT/PBAT-Co-PHA/PHA layer is 0.080 ~ 0.600mm.PLA
Described PBAT, its density is 1.23 ± 0.03g/cm3 (in specifying by GB/T 1033.1-2008, A method is tested); Melt mass flow rate is 0.5 ~ 20g/10min (testing by GB/T 3682-2000 regulation, test temperature 190 DEG C, nominal load 2.16kg), fusing point 110 ~ 145 DEG C (testing by GB/T 19466.3-2004); Biological decomposition rate>=60% (testing by GB/T 19277.1-2011 method); OTR oxygen transmission rate is 600cm
3/ m
224hatm, carbon dioxide transmitance are 600cm
3/ m
224hatm, water vapour permeability are 400g/ (m
2.24h), three kinds of gas membrane test samples are PBAT melting cast film, film thickness 0.010mm, testing according to GB/T 1038-2000 method of oxygen and carbon dioxide transmitance, water vapour permeability is tested by GB/T 1037-1988 method.
Described PPC, its density is 1.23 ~ 1.32g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested); Melt mass flow rate is 0.5 ~ 20g/10min (testing by GB/T 3682-2000 regulation, test temperature 170 DEG C, nominal load 2.16kg); Heat decomposition temperature (T5%)>=200 DEG C (measuring by SN/T 3003-2011 method); Biological decomposition rate>=60% (testing by GB/T 19277.1-2011 method); OTR oxygen transmission rate is 20cm
3/ m
224hatm, carbon dioxide transmitance are 6000cm
3/ m
224hatm, water vapour permeability are 30g/ (m
2.24h), three kinds of gas membrane test samples are PPC melting cast film, film thickness 0.010mm, testing according to GB/T 1038-2000 method of oxygen and carbon dioxide transmitance, water vapour permeability is tested by GB/T 1037-1988 method.
Described PLA, its density is 1.25 ± 0.05g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested); Melt mass flow rate is 0.5 ~ 20g/10min (testing by GB/T 3682-2000 regulation, test temperature 190 DEG C, nominal load 2.16kg); Fusing point>=125 DEG C (testing by GB/T 19466.3-2004); Biological decomposition rate>=60% (testing by GB/T 19277.1-2011 method); OTR oxygen transmission rate is 150 ~ 1200cm
3/ m
224hatm, carbon dioxide transmitance are 300 ~ 2000cm
3/ m
224hatm, water vapour permeability are 120-700g/ (m
2.24h), three kinds of gas membrane test samples are PLA melting cast film, film thickness 0.010mm, testing according to GB/T 1038-2000 method of oxygen and carbon dioxide transmitance, water vapour permeability is tested by GB/T 1037-1988 method.
Described PHA, can be at least one of PHBV (HV≤12%), PHBH (HH≤15%), PHB, P (3HB, 4HB) (4HB≤15%), wherein the density of PHBV and PHB be 1.22 ~ 1.25g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested), the density of PHBH is 1.10 ~ 1.20g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested), the density of P (3HB, 4HB) is 1.18 ~ 1.28g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested); The melt mass flow rate of PHA is 0.5 ~ 20g/10min (testing by GB/T3682-2000 regulation, test temperature 190 DEG C, nominal load 2.16kg); The fusing point 165 ~ 180 DEG C (testing by GB/T19466.3-2004) of PHB and PHBV, the fusing point 100 ~ 150 DEG C (testing by GB/T 19466.3-2004) of PHBH, the fusing point 110 ~ 160 DEG C (testing by GB/T 19466.3-2004) of P (3HB, 4HB); Biological decomposition rate>=60% (is tested by GB/T 19277.1-2011 method; OTR oxygen transmission rate is 30 ~ 200cm
3/ m
224hatm, carbon dioxide transmitance are 50 ~ 150cm
3/ m
224hatm, water vapour permeability are 5 ~ 300g/ (m
2.24h), three kinds of gas membrane test samples are PHA melting cast film, film thickness 0.010mm, testing according to GB/T 1038-2000 method of oxygen and carbon dioxide transmitance, water vapour permeability is tested by GB/T 1037-1988 method.
Absolute oral degradation rate >=60% of described multilayer material and Relative biological resolution ratio >=90% (testing by GB/T 19277.1-2011 method).
Described plural layers or sheeting, its OTR oxygen transmission rate can from 0.5 ~ 1200cm
3/ m
2adjustable between 24hatm, carbon dioxide transmitance can from 45 ~ 5000cm
3/ m
2adjustable between 24hatm, water vapour permeability can from 5 ~ 1000g/ (m
2.24h) adjustable between.Wherein the testing according to GB/T 1038-2000 method of oxygen and carbon dioxide transmitance, water vapour permeability is tested by GB/T 1037-1988 method.
Described plural layers or the preparation method of sheet material, be by each underlying biological degradative resin raw material drying and chain extender mixing after, the granulation of twin-screw reactive extrursion, obtain blends particles obtain film or sheet material through multi-layer co-extruded curtain coating or multilayer extrusion blow again.
Above-mentioned arbitrary multilayer material can be used for packaging material and the goods such as packaging, medical packaging, agriculture covering mulch film, daily plastic bag of food.
Compared with prior art beneficial effect of the present invention is:
(1) the layers of material resin of multilayer material is blending resin, it is through chain extending reaction and extrudes and directly to obtain, because the copolymer containing base resin in adjacent two layers in structure is as compatilizer, to make between this one polymer of multilayer material and layer by layer between there is good compatibility and caking property, thus make that the physical property of multilayer material is stable, not easily layering;
(2) multilayer material obtained not only can biodegradation, and oxygen, carbon dioxide and water vapour permeability can according to needs that are packaging or covering, regulated by the change changing resin content change, each layer thickness in each layer, thus realize the adjustable kinetic energy of gas.
Owing to having possessed above-mentioned advantage, make multilayer material as the substitute of conventional plastic packaging material and mulch film, and be widely used for packaging material and the goods such as packaging for foodstuff, medical packaging, agriculture covering with plastic film and daily plastic bag.
Detailed description of the invention
Below the specific embodiment of the present invention is described in further detail.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
(1) PBAT/PBAT-Co-PPC/PPC layer blending resin preparation in embodiment
A, prepare following raw material:
PBAT, PPC, according to often kind of mass percentage 10 ~ 90% ratio, mix; Be placed in drying oven by said mixture material and dry, baking temperature is 40 DEG C-60 DEG C, and drying time is 2-24 hour;
After B, drying, according to the mixed material of 100 weight portions, add the chain extender (using epoxies reactive compatibilizer in the present embodiment) of 0.1 ~ 10 weight portion, mix raw material in high-speed mixer, the mixed at high speed time is 3-30 minute;
C, the raw material after mixed at high speed is joined in double screw extruder; the screw diameter of twin-screw is 45mm; screw slenderness ratio is 36; the feeding section temperature of double screw extruder is 80-120 DEG C; compression, plasticizing and conversion zone temperature are 110-190 DEG C; die temperature is 130-190 DEG C; the screw speed of double screw extruder is 50-220rpm; obtain PBAT/PBAT-Co-PPC/PPC blending resin through double-screw extruding pelletizing, in blending resin, PBAT is 20 ~ 80%, PPC is 20 ~ 80%, PBAT-Co-PPC is 1 ~ 20%.
(2) PBAT/PBAT-Co-PLA/PLA layer blending resin preparation in embodiment
A, prepare following raw material:
PBAT, PLA, according to often kind of mass percentage 10 ~ 90% ratio, mix; Be placed in drying oven by said mixture material and dry, baking temperature is 40 DEG C-90 DEG C, and drying time is 2-24 hour;
After B, drying, according to the mixed material of 100 weight portions, add the chain extender (using epoxies reactive compatibilizer in the present embodiment) of 0.1 ~ 10 weight portion, mix raw material in high-speed mixer, the mixed at high speed time is 3-30 minute;
C, the raw material after mixed at high speed is joined in double screw extruder; the screw diameter of twin-screw is 45mm; screw slenderness ratio is 36; the feeding section temperature of double screw extruder is 80-120 DEG C; compression, plasticizing and conversion zone temperature are 110-190 DEG C; die temperature is 130-190 DEG C; the screw speed of double screw extruder is 50-220rpm; obtain PBAT/PBAT-Co-PLA/PLA blending resin through double-screw extruding pelletizing, in blending resin, PBAT is 20 ~ 80%, PLA is 20 ~ 80%, PBAT-Co-PLA is 1 ~ 20%.
(3) PBAT/PBAT-Co-PHA/PHA layer blending resin preparation in embodiment
A, prepare following raw material:
PBAT, PHA, according to often kind of mass percentage 10 ~ 90% ratio, mix; Be placed in drying oven by said mixture material and dry, baking temperature is 40 DEG C-90 DEG C, and drying time is 2-24 hour;
After B, drying, according to the mixed material of 100 weight portions, add the chain extender (using epoxies reactive compatibilizer in the present embodiment) of 0.1 ~ 10 weight portion, mix raw material in high-speed mixer, the mixed at high speed time is 3-30 minute;
C, the raw material after mixed at high speed is joined in double screw extruder; the screw diameter of twin-screw is 45mm; screw slenderness ratio is 36; the feeding section temperature of double screw extruder is 80-120 DEG C; compression, plasticizing and conversion zone temperature are 110-190 DEG C; die temperature is 130-190 DEG C; the screw speed of double screw extruder is 50-220rpm; obtain PBAT/PBAT-Co-PHA/PHA blending resin through double-screw extruding pelletizing, in blending resin, PBAT is 20 ~ 80%, PHA is 20 ~ 80%, PBAT-Co-PHA is 1 ~ 20%.
(4) three-layer co-extruded cast film preparation
A. (in this example, PBAT mass percentage is 60% to PBAT/PBAT-Co-PPC/PPC blending resin step (1) obtained, PBAT-Co-PPC mass percentage is 5%, PPC mass percentage is 35%) join in No. two single screw extrusion machines (intermediate layer extruder) of three-layer co-extruded equipment, one district's temperature of single screw extrusion machine is 110-150 DEG C, two district's temperature are 130-190 DEG C, three district's temperature are 130-190 DEG C, and die temperature is 130-190 DEG C;
B. (in this example, PBAT mass percentage is 60% to PBAT/PBAT-Co-PLA/PLA blending resin step (2) obtained, PBAT-Co-PLA mass percentage is 5%, PLA mass percentage is 35%) join in a single screw extrusion machine of three-layer co-extruded equipment, one district's temperature of single screw extrusion machine is 110-150 DEG C, two district's temperature are 130-190 DEG C, three district's temperature are 130-190 DEG C, and die temperature is 130-190 DEG C;
C. (in this example, PBAT mass percentage is 60% to PBAT/PBAT-Co-PHA/PHA blending resin step (3) obtained, PBAT-Co-PLA mass percentage is 5%, PLA mass percentage is 35%) join in No. three single screw extrusion machines of three-layer co-extruded equipment, one district's temperature of single screw extrusion machine is 110-150 DEG C, two district's temperature are 130-190 DEG C, three district's temperature are 130-190 DEG C, and die temperature is 130-190 DEG C;
D. the melt that above three single screw extrusion machine mouth moulds flow out is entered three-layer co-extrusion tape casting machine head, head temperature is 130-190 DEG C, control the rate of feeding of each single screw extrusion machine, screw speed and casting machine draught animals film gap thereof, the thickness of each layer film is made to be respectively 0.020mm, the gross thickness of multilayered film material is 0.060mm, and three-layer co-extruded film is denoted as [PBAT/PBAT-Co-PLA/PLA]/[PBAT/PBAT-Co-PPC/PPC]/[PBAT/PBAT-Co-PHA/PHA].
(5) three-layer co-extruded cast film biodegradability and gas permeation rate
A. as a comparison, PBAT, PLA, PHA, PPC is used to prepare respective three-layer co-extruded cast film respectively according to step (4), co-extrusion plural layers thickness is 0.060mm (each layer thickness is 0.020mm), be denoted as PBAT/PBAT/PBAT, PLA/PLA/PLA, PHA/PHA/PHA, PPC/PPC/PPC respectively;
B. carry out degradation property test to the plural layers obtained by GB/T 19277.1-2011 method, Absolute oral degradation rate is the test result of film itself, and Relative biological resolution ratio is that Absolute oral resolution ratio is divided by the cellulosic Absolute oral resolution ratio of reference material;
C. by GB/T 1038-2000 method, OTR oxygen transmission rate and carbon dioxide transmission measurement are carried out to the various three-layer co-extruded cast film obtained;
D. by GB/T 1037-1988 method, water vapour permeability test is carried out to the various three-layer co-extruded cast film obtained;
Biological degradation rate, OTR oxygen transmission rate, carbon dioxide transmitance, water vapour permeability test result are as shown in table 1.
Table 1
Embodiment 2-7
(1) by the step (1) in embodiment 1, (2), (3) [PBAT/PBAT-Co-PLA/PLA] blend layer is prepared respectively, [PBAT/PBAT-Co-PPC/PPC] blend layer, [PBAT/PBAT-Co-PHA/PHA] blend layer, (in this example, PBAT mass percentage is 60% to the PBAT/PBAT-Co-PPC/PPC blending resin obtained, PBAT-Co-PPC mass percentage is 5%, PPC mass percentage is 35%), (in this example, PBAT mass percentage is 60% to the PBAT/PBAT-Co-PLA/PLA blending resin obtained, PBAT-Co-PLA mass percentage is 5%, PLA mass percentage is 35%), (in this example, PBAT mass percentage is 60% to the PBAT/PBAT-Co-PHA/PHA blending resin obtained, PBAT-Co-PLA mass percentage is 5%, PLA mass percentage is 35%),
(2) prepare three-layer co-extruded curtain coating by the step (4) in embodiment 1 thin, measure biological degradation rate, OTR oxygen transmission rate, carbon dioxide transmitance, the water vapour permeability of plural layers by the step (5) in embodiment 1.Various plural layers product composition and test result as shown in table 2.
Table 2
As can be seen from the embodiment 1-7 of table 1 and table 2, be 0.060mm in plural layers gross thickness, change the thickness of every layer film in a kind of composition situation of filling a prescription of fixing every layer, the Absolute oral degradation rate of the most total three-layer thin-film all>=80%, Relative biological resolution ratio>=90%; OTR oxygen transmission rate can be less than 100cm
3/ (m
224hatm) change between 20 ~ 100 in situation; Carbon dioxide transmission rate can be less than 500cm
3/ (m
224hatm) in situation from carrying out between 200 ~ 500 changing, water vapour permeability can be less than 50g/ (m
2.24h) change between 10 ~ 50 in situation.Visible, in the biodegradation of guarantee plural layers simultaneously, barrier property obtains and improves, and gas permeation rate can regulate.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (9)
1. the plural layers that the gas permeation rate obtained by melting co-extrusion is adjustable or a sheeting, is characterized in that material is three layers or five layers or seven layers, and the one wherein at least comprising following material is formed:
A) terephthalic acid (TPA) adipic acid butanediol copolymer (PBAT)/terephthalic acid (TPA) adipic acid butanediol copolymer-chain extender--poly (propylene carbonate) (PBAT-Co-PPC)/poly (propylene carbonate) (PPC) blend layer (PBAT/PBAT-Co-PPC/PPC);
B) terephthalic acid (TPA) adipic acid butanediol copolymer (PBAT)/terephthalic acid (TPA) adipic acid butanediol copolymer-chain extender-PLA (PBAT-Co-PLA)/PLA (PLA) blend layer (PBAT/PBAT-Co-PLA/PLA);
C) terephthalic acid (TPA) adipic acid butanediol copolymer (PBAT)/terephthalic acid (TPA) adipic acid butanediol copolymer-chain extender-PHA (PBAT-Co-PHA)/PHA (PHA) blend layer (PBAT/PBAT-Co-PHA/PHA).
2. according to right 1 requirement, it is characterized in that, chain extender used is at least one in polyoxyethylene poly-oxygen propylene aether block copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer, epoxies reactive compatibilizer, oxazoline class reactive compatibilizer, food-grade isocyanates reactive compatibilizer, and the consumption of chain extender is 0.1 ~ 10%.
3. according to right 1 requirement, it is characterized in that, various composition quality percentage composition is:
A) PBAT/PBAT-Co-PPC/PPC layer, PBAT is 20 ~ 80%, PBAT-Co-PPC is 1 ~ 20%, PPC is 20 ~ 80%;
B) PBAT/PBAT-Co-PLA/PLA layer, PBAT is 40 ~ 80%, PBAT-Co-PLA is 1 ~ 20%, PLA is 20 ~ 60%;
C) PBAT/PPBAT-Co-PHA/PHA layer, PBAT is 20 ~ 80%, PBAT-Co-PHA is 1 ~ 20%, PHA is 20 ~ 80%.
4. multilayer material according to claim 1, is characterized in that, PBAT/PBAT-Co-PPC/PPC layer is in most intermediate layer: time three-layer co-extruded, and PBAT/PBAT-Co-PPC/PPC is in most intermediate layer; During five-layer co-squeezing, PBAT/PBAT-Co-PPC/PPC layer is respectively second and the 4th layer (being followed successively by ground floor to layer 5 to innermost layer by surface); During seven-layer co-extrusion, PBAT/PBAT-Co-PPC/PPC layer respectively second, the 4th and layer 6 (being followed successively by ground floor to layer 7 to innermost layer by surface).
5., according to the multilayer material that right 1,3,4 requires, during for plural layers, it is characterized in that,
A) when many materials are plural layers, the thickness of plural layers is 0.018 ~ 0.250mm, wherein, the every layer thickness of PBAT/PBAT-Co-PPC/PPC layer is 0.006 ~ 0.050mm, the every layer thickness of PBAT/PBAT-Co-PLA/PLA layer is the every layer thickness of 0.006 ~ 0.050mm, PBAT/PBAT-Co-PHA/PHA layer is 0.006 ~ 0.050mm;
B) when multilayer material is composite wafer, the thickness of composite wafer is 0.200 ~ 1.0mm, wherein, the every layer thickness of PBAT/PBAT-Co-PPC/PPC layer is 0.060 ~ 0.600mm, the every layer thickness of PBAT/PBAT-Co-PLA/PLA layer is the every layer thickness of 0.060 ~ 0.800mm, PBAT/PBAT-Co-PHA/PHA layer is 0.080 ~ 0.800mm.
6., according to the multilayer material that right 1 ~ 5 requires, it is characterized in that,
A) density of PBAT described in it is 1.23 ± 0.03g/cm3 (in specifying by GB/T 1033.1-2008, A method is tested), melt mass flow rate is that 0.5 ~ 20g/10min (tests by GB/T 3682-2000 regulation, test temperature 190 DEG C, nominal load 2.16kg), fusing point 110 ~ 145 DEG C (testing by GB/T 19466.3-2004), biological decomposition rate >=60% (testing by GB/T 19277.1-2011 method);
B) density of PPC described in it is 1.23 ~ 1.32g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested), melt mass flow rate is that 0.5 ~ 20g/10min (tests by GB/T 3682-2000 regulation, test temperature 170 DEG C, nominal load 2.16kg), heat decomposition temperature (T5%)>=200 DEG C (measuring by SN/T 3003-2011 method), biological decomposition rate>=60% (testing by GB/T 19277.1-2011 method);
C) density of PLA described in it is 1.25 ± 0.05g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested), melt mass flow rate is that 0.5 ~ 20g/10min (tests by GB/T 3682-2000 regulation, test temperature 190 DEG C, nominal load 2.16kg), fusing point>=125 DEG C (testing by GB/T 19466.3-2004), biological decomposition rate>=60% (testing by GB/T 19277.1-2011 method);
D) PHA described in it can be PHBV (HV≤12%), PHBH (HH≤15%), PHB, P (3HB, 4HB) at least one of (4HB≤15%), wherein the density of PHBV and PHB is 1.22 ~ 1.25g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested), the density of PHBH is 1.10 ~ 1.20g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested), the density of P (3HB, 4HB) is 1.18 ~ 1.28g/cm
3(in specifying by GB/T 1033.1-2008, A method is tested), the melt mass flow rate of PHA is that 0.5 ~ 20g/10min (tests by GB/T 3682-2000 regulation, test temperature 190 DEG C, nominal load 2.16kg), the fusing point 165 ~ 180 DEG C (testing by GB/T 19466.3-2004) of PHB and PHBV, the fusing point 100 ~ 150 DEG C (testing by GB/T 19466.3-2004) of PHBH, P (3HB, fusing point 4HB) 110 ~ 160 DEG C (testing by GB/T 19466.3-2004), biological decomposition rate>=60% (is tested by GB/T19277.1-2011 method.
7., according to plural layers or the sheeting of right 1 ~ 6 requirement, it is characterized in that, OTR oxygen transmission rate can from 0.5 ~ 1200cm
3/ m
2adjustable between 24hatm, carbon dioxide transmitance can from 45 ~ 5000cm
3/ m
2adjustable between 24hatm, water vapour permeability can from adjustable between 5 ~ 1000g/ (m2.24h).Wherein the testing according to GB/T 1038-2000 method of oxygen and carbon dioxide transmitance, water vapour permeability is tested by GB/T 1037-1988 method.
8. the preparation method of the arbitrary plural layers according to claim 1-7, is characterized in that comprising the following steps: the blends particles of each underlying biological degradative resin raw material drying and chain extender mixing, the granulation of twin-screw reactive extrursion, acquisition is obtained film or sheet material through multi-layer co-extruded curtain coating or multilayer extrusion blow again.
9., according to right 1 ~ 8 requirement, arbitrary multilayer material can be used for packaging material and the goods such as packaging, medical packaging, agriculture covering mulch film, daily plastic bag of food.
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